Compounded oil



Patented Jan. 14,1941

Elmslie W. Gardiner and George H. Denison,

Berkeley, Calif., assixnors to Standard Oil Company of California, San Francisco, Calif., a. corporation of Delaware No Drawing. Application October Serial No. 234,047

14 Claims.

This invention relates to new and useful compositions of matter and involves more particularly a composition comprising a hydrocarbon oil and an alkaline earth metal phenate of high moiecular weight.

The production of improved hydrocarbon oils, and particularly of lubricatalg oils having desired characteristics, has been the subject of extensive research and investigation in recent years. Generally speaking, the compounding of hydrocarbon pirical phenomena, and the action of untested types of compounding agents cannot be predicted.

A characteristic which has been. the subject of extensive investigation is the tendency of hydrocarbon oils to deteriorate or partially decompose when subjected to high temperatures. This deteriorationis evidenced by the deposition of adhesive deposits on hot metallic surfaces over which the hydrocarbon oil may flow. It is important that resistance to such deterioration be imparted to hydrocarbon oils, particularly to lubricating oils, in order that such compositions may be relatively free from the tendency to form such deposits even under high temperatures and severe operating conditions. A direct result of this type of deterioration during lubrication of internal combustion engines, such as engines of the Diesel type, is the tendency of the oil to 3 cause or permit the sticking of piston rings.

Compounds which render hydrocarbon oils more resistant to deterioration by heat at high temperature levels usually, though not always, impart to the oil the ability to inhibit piston n'ng stick- 35 ing in internal combustion engines and permit longer periods of operation of such engines without the necessityof major overhauls heretofore occasioned by stuck piston rings.

It has been discovered thatdispersion of alkaline earth metal phenates in hydrocarbon oils such as mineral lubricating oil imparts newand unpredictable properties thereto. 'I 'hese new properties render the compounded oil particularly useful for various purposes. For example, oil-soluble alkaline earth phenates like calcium lauryl phenates, calcium cetyl phenates, calcium di-amyl phenate and calcium heptyl phenate are capable of inhibiting piston ring sticking when incorporated in crankcase lubricants for internal combustion engines such as Diesel engines.

In general, it has been discovered that the new compositions herein disclosed are more stable to heat than is the hydrocarbon oil from which the compositions are compounded. The alkaline 55 earth metal phenates are capable of imparting to oils to obtain desired characteristics involves emmineral lubricating oils the property of resistance to sludge .formation and to the deposition oi lacquer or gum-like materials on metal surfaces at high temperatures, such as 425 F. to 550 F., encountered in the ring belt zone of Diesel engines. 5 The new compositions of this invention are therefore particularly useful where resistance to heat is important. In addition to having outstanding advantages as a lubricant for pistons and piston rings of internal combustion engines, the present 10 composition is useful as a heat transfer nuid Where it may be desirable to inhibit or prevent the formation of avdeposit on the metal surface from or to which heat is being conveyed.

It has also been discovered that calcium phel5 nates in particular have a combination of properties heretofore unknown and particularly desir-, able in compounded lubricating oils, namely, the ability to impart resistance to deterioration by heat or the ability to inhibit piston ring sticking,

the ability to reduce wear on cylinder walls and, piston rings of internal combustion engines as compared with the wear produced by conventional uncompounded mineral oils, and non-corrosivity of the compounded oil as respects its chemical action on bearing metals such as cadmium-silver alloys. Although various compounded mineral oils are known which are capable of inhibiting piston ring sticking, the discovery of specific compounding agents capable of imparting 30 the above combination of properties .to hydrocarbon oils represents an unobvious and important discovery.

Examples of alkaline earth metal phenates which may be added to hydrocarbon oils such as mineral oils to provide a new ccimposition of matter of the type herein involved comprise magnesium phenates, barium phenates, strontium phenates and calcium phenates.

The phenates of this invention are preferably formed from high molecular weight alkyl phenols of the type formulaaralkyl, alkaryl or cyclic non-benzenoid groups,

10 Compounds containing one or more alkyl groups are contemplated. For example, either mono--- I alkyl phenolic or di-alkyl phenolic radicals may be utilized in the present invention.

To guide those skilled in the art in the preparation oi the compositions of this invention, the following specific examples oi methods oi preparing alkyl phenols are submitted:

Example 1.An alkyl phenol desirableior present purposes may be prepared as follows: Phenol and a butene polymer, having an apparent molecular weight oi 194 ,and obtained by p lymerization of a mixture oi butenes containing butene- 1, butene-2, and iso-butene, were mixed. To this mixture, containing 237 grams of phenol and 500 25 grams oi the above mentioned butene polymers, 140 cubic centimeters of 94% sulfuric acid were added slowly with agitation. The temperature was kept below 65 F. during addition oi the acid. The mixture was agitated for two hours after the addition oi acid was completed and permitted to come to room temperature. The reaction product was then diluted with an equal volume oi water and placed in a sealed autoclave where it was heated at 350 F. for an hour with agitation. The product was .washed with water, sodium carbonate solution and again with water in order to free itoi sulfuric acid, sulfonates and unreacted phenol. A 93% yield of high molecular weight water-insoluble alkyl 40 phenol having an acetyl number oi 181 was obtained.

Example 2.5l1 grams oi crude cresyiic acid, 900 grams oi oleilne polymers containing an aver-'- age oi 14 carbon atoms per molecule, and 4'75 45 grams of 98% sulfuric acid were utilized in preparing an alkylated cresol. These ingredients were combined and treated in the manner described above for preparation of cetyl phenol.

The product was vacuum-distilled at mm.

and a 50 to 90% cut of an alkyl phenol obtained which had a molecular weight oi 291 and was used to prepare the calcium salt hereinafter described in Example 6.

It is to be understood that the above examples 55 are given by way oi illustration only and that other condensation reactions utilizing alcohols, alkyl chlorides and the like, rather than oleflnes, may be adopted as a starting material for introducing the alkyl group into' the aromatic nu- 60 cleus. Also other known condensation agents, such as aluminum chloride, zinc chloride, etc., may be adopted for eiiecting the alkylation reaction. A mixture oi sulfuric and glacial acetic acids may be used with advantage as a condens- 65 ing agent. 'A suitable mixture comprises 100 parts by weight 98% H2504 to 60 parts by weight oi glacial acetic acid. The presence oi the acetic acid facilitates temperature control and gives a softer, easier handled reaction product.

The following comprise illustrative examples oi the preparation oi alkaline earth metal phenates oi this invention:

Example 3.24'l grams of an alkylated phenol having an apparent molecular weight of 247 were agitated for six hours at 500 F. with 64 grams of powdered calcium carbide. A gaseous reaction product containing acetylene was formed and removed. The product remaining in the reaction zone was a dark-colored brittle solid at room temperature and comprised a calcium salt of the 5 alkylated phenol. 94% oi the theoretical yield of calcium phenate was obtained as shown by an analysis oi a sample of the reaction productfreed from calcium carbide by filtration of its petroleum ether solution.

Esample 4.685 grams of an alkylated phenol having an apparent molecular weight of 290 were agitated ior six hours at from approximately 500' F. to 540 1''. with 90 grams of calcium carbide. A gas containing acetylene was formed and re- 15 moved. The product remaining in the reaction zone was a dark-colored brittle solid at room temperature. A yield of calcium phenate, representing 96% oi that theoretically possible, was

obtained. Example 5.-44 grams of p-cyclohexyl phenol and 20 grams of powdered calcium carbide were heated together at 350 1''. for one hour. The product was a tan-coloredpowder insoluble in petroleum ether, soluble in benzene, and comprising the calcium salt of p-cyclohexyl phenol.

Example 6,-234 grams of an alkyl cresol (molecular weight 291) and 25 grams of powdered calcium carbide were heated at 530 F. with stirring for iour hours. The product obtained comso prising the calcium salt of alkyl cresol was a hard brittle solid, soluble in mineral oil.

It is believed that the reaction occurring in the above examples may be represented by the iollowins equation:

caca-l-zn-clmon-mnn+cam-ctmo)a The other alkaline earth metal carbides give this type reaction which may be utilized in their prep! aration. 1

Additional examples of methods of preparing alkaline earth metal phenates useful in the compositions of this invention comprise the following:

Example 7.-500 grams of an alkyl phenol (molecular weight 290) was heated to 520 to 540' F. and a crystal of iodine was added. grams of magnesium turnings were then incorporated in small increments to maintain a rapid but safe evolution of hydrogen. Before the entire quantity oi magnesium has been added, the reaction mixture became too viscous to stir even at 600 F. This mixture was dissolved in acid treated S. A. E. 30 Western lubricating oil and topped to 480 F. at 5 mm. pressure in a still.

Example 8.'l.6 grams of barium hydroxide were dissolved in 7 cc. of water at 212 F. To this was added, with agitation, about 5 grams of cetyl phenol and 7 cc. of ethyl alcohol to promote solution of the cetyl phenol and facilitate reaction. The mixture was boiled for about three minutes, extracted with a hydrocarbon thinner, the extract illtered and the thinner evaporated. The product obtained was an amber, brittle semisolid containing approximately 65% of the barlum salt of cetyl phenol. The reaction product as obtained was dissolved as a 1% solutionin lubricating oil and found by engine test to satisiactorily inhibit piston ring sticking.

The proportion of alkaline earth metal phenates added to mineral oils may vary widely depending upon the uses involved and the properties-desired. As little as 0.1% by weight oi the phenate gives measurable improvements, although irom approximately 0.25 to approximate- 7'5 1y 2% phenate ispreierred where thexcompounded 011 is to be used as a crankcase lubricant for internal combustion engines. As much as 50% by weight of various of the phenates may be dissolvedin mineral oil for the P rpose of preparing a concentrate capable of dilution with lubricating oils and the like; Other solvents such as ethers, esters and the like may be used for preparing these concentrates. comprise a convenient method of handling the phenates and may be used as a compounding agent for lubricants in general, as well as for other purposes.

The advantages of the compounded mineral oil of this invention are shown by the following data:

Such concentrates in the same test with the same oil containing 1% calcium cetyl phenate, the wear was only 105 units. In the kinetic machine the wear at 400 1''. was 193 units with'the uncompound oil, as against 15 units with the same 011 cont" g 1% calcium cetyl phenate. I

The alkaline earth metal phenates or this invention maybe added to mineral oils containing other compounding ingredients, such as pour point depressors, oiliness agents, extreme pressure addition agents, corrosion inhibitors, bloom- .in'g agents. compounds for increasing the viscos- Time to stick rings Used oil inspections 3223:: Relative Relative o in hi c1521? Vi Vi N t Remarks om m car n ass a. s. eu 0H" lags 100 F. 210 No.

Acid refined. S. A. E. 30, 1.0 Very low.. Pool Poor 906 64.3 0. 72 I Western oil-No. l.

Oil No.1plus 1% barium 45+ 1.5+ Low..-.. Good Fair 1,045 57.1 0.99 Made by reaction with cetyl phenate. barium hydroxide. Oil No. 1 plus 1.1% cal- 90+ 3.0+ Very low.. Excellent. Very good 1, 490 70. 7 3.87 Made withcalcium metal,

cium cetyl phenate. and cetyl phenol. Oil No. 1 plus 1.0% cal- 165+ 5.5+ do Periect. .do 1,915 86.2 3.90 Check run on above.

cium cetyl phenate. Oil No. 1 plus .88% cal- 135+ 4. 5+ .do..- ...do Good 1, 576 79.7 3.63 Made from calcium carcium cetyl phenate. hide and eetyl phenol. Oil No. 1 plus 0.5% cal- 120+ 4.0+ Low Very good. Fair 1,764 84. l 3.54 Made irom calcium metcium cetyl phenate. al and cetyl phenol. Oil No. 1 plus 0.96% cal- 120 4.0 Medium. ..do Good 1.480 57.9 3. 45 Cetyl phenol made by cium cetylphenate. alutililiitiiium chloride me o S.A.E.30,WesternOil- 45+ 1. 5+ Fair Poor l, 000 58. 7 l. 42 0.74% calcium cetyl Tests on compounding phenate. agent in diilerent oil. Oil No. 2 plus 1.22% 081- 105 3.5 Very low- Good Verygood. r 1,060 70.9 1.85

cium cetyl phenate. v Oil No. 1 plus 1% calcium 60 2.0 do ...do. Fair l, 250 72. 5 2.06 Made with calcium metdi-amyl honate. al and di-amyl' phenol. Oil N 0- F 8 l%c lc1um 60+ 2. 0+ High do..... ..do l, 425 75. 7 3. 01 Made with calcium met- "hepty phenate. a} and heptyl" pheno 'Oil No. 2 plus 1.55% cal- 120+ 4. 0+ Medium. Excellent.. Good. 1, 107 72. 2 0. 81 Made with calcium metcium lauryl phenate. al and lauryl phenol. Oil No. 1 plus 1% cal- 1.5 Very low- Fair Fair 1,150 69.2 1.87 Made with calcium metcium p-tertiary amyl iii and tertiary amyl phenate. phenol. 45

' Corrosion data not from engine test.

"Ratio of time required to stick rings with compounded oil as compared with uncompounded mineral oil.

In the above piston ring sticking tests, a single cylinder 2%" bore, 2 /2" stroke, Lauson gasoline engine was operated under extremely severe conditions for the purpose of developing fully piston ring sticking and piston gumming tendencies under circumstances simulating severe operating conditions encountered in the field. Operation of the motor during tests was continuous at 1600 R. P. M. except for periodic shut-downs at fifteen-hour intervals for inspection; the jacket temperature was maintained at 345 F. and sump 6 oil temperature at 220 F. The corrosion data given, except where noted otherwiseywere determined by measuring the loss of weight of metal from the bearings during runs withthis' type of engine under the above severe conditions.

The ability of the calcium phenates to reduce or prevent wear is illustrated by tests in a Weeks. machine and a kinetic B machine. (The Weeks machine is similar to the Timken testing machine described in S. A. E. Journal, vol. 28, page 53, 1932, and the kinetic 13" testing machine is described section 3, page 60, of A. P. I.

Proceedings, Mid-Year 1932, published by the American Petroleum Institute). In the Weeks machine an acid refined Western 011, S. A/E. 30, 75 permitted a wear of 288 units at 300 F. where,

only metal phenates but thickening agents or metal soaps present either in grease-forming proportions or in amounts insumcient to form greases, as in the case. of mineral castor 'machine oils.

While the character of this invention has been described in detail, and numerous examples of the preparation and application of the composition'given, this has been done by way of illustration only and with the intention that no limitation should be imposed on the invention thereby. It will be apparent to those skilled in the art that numerous modifications and variations of the illustrative examples may be effected in the practice of the invention which is of the imately by weight based on the oil of an alkaline earth metal phenate containinga radical oi the type Iormula-- v in which R is an alkyl group having at least five carbon atoms.

4. A composition as defined in claim 3, in which the alkaline earth metal is calcium.

5. A lubricating composition comprising a mineral oil and from approximately 0.1 to approximately 50% by weightbased on the oil oi. an alkaline earth metal phenate dissolved therein, said phenate containing a substituted phenolic radical having more than ten carbon atoms.

6. A lubricating composition as defined in claim 5, in which said alkaline earth metal is calcium.

7. A lubricating composition comprising a mineral lubricating oil and a small amount suificient substantially to inhibit deterioration of said lubricating oil at elevated temperatures of an alkaline earth metal phenate containing a radical oi! ,the type formula in which R is an allwl group containing at least five carbon atoms.

8. A lubricating composition comprising a mineral lubricating oil as defined in claim '7, in which the alkaline earth metal is calcium.

9. A liquid lubricating oil comprising a mineral oil and an alkaline earth metal phenate capable of inhibiting piston ring sticking in internal combustion engines when added to the crankcase lubricants thereo! in an amount comprising i'rom approximately 0.25 to 2% by weight of the lubricating oil, said phenate containing eating oil.

a phenolic radical having a hydrocarbon substituent in the aromatic nucle selected from the class consisting or alkyl. ary alkaryl, aralkyi and cyclic non-benzenoid groups. 1

10. A liquid lubricating composition as defined in claim 9, in which the alkaline earth metal is calcium. I

11. A liquid lubricating oil comprising a hydrocarbon oil normally having the tendency to cause piston ring sticking in internal combustion engines, such as Diesel engines, and a small amount of an alkaline earth metal phenate having a phenolic radical containing a hydrocarbon substituent' with at least five carbon atoms, said phenate being present in the oil in an amount 1 suflicient substantially to inhibit piston ring sticking.

12. A liquid lubricating oil comprising a hydroi carbon oil normally having the tendency to cause piston ring sticking in internal combustion engines, such as Diesel engines, and a small amount of an alkylated phenate 01 an alkaline earth metal, said phenate being present in the oil in an amount sufllcient substantially to inhibit piston ring sticking.

13. An anti-ring-sticking addition agent for lubricating oils comprising a concentrated solution in hydrocarbon oil of an alkaline earth metal phenate containing a substituted phenolic radical having more than ten carbon atoms, said phenate being eflective to inhibit piston ring sticking in a crankcase lubricant oi. an internal' combustion engine, said concentrate being capable of dilution with hydrocarbon lubricating oil to form a homogeneous mixture containing from approximately 0.25% to approximately 2% by weight of said phenate based on the lubri- 14. An anti-ring-sticking addition agent for crankcase lubricating oils comprising an alkaline earth metal phenate containing a phenolic rad-l ical having an alkyl portion of at least five carbon atoms.

ELMSLIE W. GARDINER. GEORGE H. DENISON, JR. 

